CA2983604A1 - Method for preparing negative electrode material of lithium-ion battery by using biomass gasification furnace filter residue - Google Patents
Method for preparing negative electrode material of lithium-ion battery by using biomass gasification furnace filter residueInfo
- Publication number
- CA2983604A1 CA2983604A1 CA2983604A CA2983604A CA2983604A1 CA 2983604 A1 CA2983604 A1 CA 2983604A1 CA 2983604 A CA2983604 A CA 2983604A CA 2983604 A CA2983604 A CA 2983604A CA 2983604 A1 CA2983604 A1 CA 2983604A1
- Authority
- CA
- Canada
- Prior art keywords
- residue
- lithium
- filter residue
- washing
- filtering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002028 Biomass Substances 0.000 title claims abstract description 22
- 239000007773 negative electrode material Substances 0.000 title abstract description 5
- 238000002309 gasification Methods 0.000 title abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005406 washing Methods 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 239000010405 anode material Substances 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 229950004959 sorbitan oleate Drugs 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- -1 lauryl diphenyl ether Chemical compound 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 230000010355 oscillation Effects 0.000 abstract 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 description 27
- 239000003575 carbonaceous material Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021385 hard carbon Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- ZNHNOZBMSGSAGE-UHFFFAOYSA-N hexadecane-1-sulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCS(O)(=O)=O ZNHNOZBMSGSAGE-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Disclosed is a method for preparing a negative electrode material of a lithium-ion battery by using a biomass gasification furnace filter residue. The method comprises: 1) mixing a biomass gasification furnace filter residue with a surface active agent and grinding the mixture, grinding the mixture adequately, removing the surface active agent in a water washing manner, carrying out the suction filtration, and obtaining the filter residue for standby use; 2) placing hydrochloric acid into the filter residue obtained in step 1), adequately removing impurities, and filtering and washing the filter residue to be neutral for standby use; 3) placing the filter residue obtained in step 2) into a mixed solution of polyethyleneimine and ethanol, carrying out the oscillation, washing the polyethyleneimine and the ethanol after the adequate oscillation, performing the filtering, and obtaining the filter residue for standby use; and 4) placing nitric acid having a mass fraction of 55% to 70% into the filter residue obtained in step 3), adequately stirring at the temperature of 35 to 45 degrees centigrade, carrying out the modification, washing the nitric acid, and filtering and drying to obtain a negative electrode material of a lithium-ion battery. The negative electrode material of the lithium-ion battery, which has a high capacity, a high primary efficiency and good cycling performance and is safe and pollution-free, is obtained; the process is simple in process flow, low in cost and applicable to the expanded production.
Description
METHOD FOR PREPARING NEGATIVE ELECTRODE MATERIAL OF
LITHIUM-ION BATTERY BY USING BIOMASS GASIFICATION FURNACE
FILTER RESIDUE
FIELD OF THE INVENTION
[0001] The invention relates to a technique thr producing lithium-ion battery materials, and more particularly to a method for preparing an anode material for lithium-ion batteries using residues from biomass gasifiers of biomass synthetic oil refineries.
BACKGROUND OF THE INVENTION
=
LITHIUM-ION BATTERY BY USING BIOMASS GASIFICATION FURNACE
FILTER RESIDUE
FIELD OF THE INVENTION
[0001] The invention relates to a technique thr producing lithium-ion battery materials, and more particularly to a method for preparing an anode material for lithium-ion batteries using residues from biomass gasifiers of biomass synthetic oil refineries.
BACKGROUND OF THE INVENTION
=
[0002] Since lithium-ion batteries have the advantages such as high energy, high working voltage, low self discharge, wide operating temperature range, no memory effect, environmental protection and long service life, lithium-ion batteries are widely used in various fields including mobile phone, computer, digital camera, electric vehicle, hybrid power automobile, new energy automobile, ship dynamics and aerodynamics fields.
[0003] The anode materials for lithium-ion batteries have a great influence on the safety, cycle life and energy density of lithium-ion batteries. At present, the anode materials for lithium-ion batteries mainly are carbon materials, tin-based materials, silicon materials and lithium titanate. Due to the poor cycle stability of tin-based materials, the severe volume effect of silicon materials and the low capacity and high cost of lithium titanate, the commercial anode materials for lithium-ion batteries are mainly carbon materials. The carbon anode materials include natural graphite, artificial graphite, mesocarbon =
microbeads and hard carbon materials. ate to the higher capacity, good rate capability, good cycle performance and good safety performance of its irregular sequencing, hard carbon materials have become the hot research topic.
microbeads and hard carbon materials. ate to the higher capacity, good rate capability, good cycle performance and good safety performance of its irregular sequencing, hard carbon materials have become the hot research topic.
[0004] The common hard carbon materials mainly include resin carbon, pyrolytic carbon of organic polymers and carbon microbeads by hydrothermal synthesis.
The main raw material sources of hard carbon materials are polymer compounds and fossil fuel asphalt. The hard carbon materials used as the anode materials for lithium-ion batteries have the following disadvantages that: (1) its polymer compound materials have a high cost and are prone to environmental pollution; and (2) the first-cycle coulombic efficiency of the hard carbon materials is lower.
SUMMARY OF THE INVENTION
The main raw material sources of hard carbon materials are polymer compounds and fossil fuel asphalt. The hard carbon materials used as the anode materials for lithium-ion batteries have the following disadvantages that: (1) its polymer compound materials have a high cost and are prone to environmental pollution; and (2) the first-cycle coulombic efficiency of the hard carbon materials is lower.
SUMMARY OF THE INVENTION
[0005] It is one objective of the invention to provide a method for preparing an anode material for lithium-ion batteries using residues from biomass gasifiers of biomass synthetic oil refineries. Through the method, economical, green and clean anode materials for lithium-ion batteries are prepared, and the resulting anode materials have a relatively high first-cycle coulombic efficiency.
[0006] To achieve the above objectives, in accordance with one embodiment of the invention, there is provided a method for preparing an anode material for lithium-ion batteries using a residue from a biomass gasifier, and the method comprising:
[0007] (1) mixing a raw residue from a biomass gasifier and an aqueous solution comprising a surfactant to yield a mixed solution, fully grinding the mixed solution to disperse the raw residue, washing the mixed solution using water to remove the surfactant, leaching the mixed solution and collecting a first intermediate residue for use;
[0008] (2) adding hydrochloric acid to the first intermediate residue obtained in (1), stirring to remove impurities, filtering, arid washing the residue to be neutral, to yield a second intermediate residue for use;
[0009] (3) adding polyethyleneimine and ethanol to the second intermediate residue obtained in (2), shaking to disperse the second intermediate residue, washing away the polyethyleneiraine and the ethanol, filtering, to yield a third intermediate residue for use; and
[0010] (4) adding nitric acid having a mass fraction of between 55% and 70%
to the third intermediate residue obtained in (3), fully stirring at a temperature =
ranging between 35 C and 45 C for oxidation and modification, washing away the nitric acid, filtering and drying, to yield the anode material for lithium-ion batteries.
to the third intermediate residue obtained in (3), fully stirring at a temperature =
ranging between 35 C and 45 C for oxidation and modification, washing away the nitric acid, filtering and drying, to yield the anode material for lithium-ion batteries.
[0011] In a class of this embodiment, in (1), the surfactant is sodium dodecyl benzene sulfonate, 1-hexadecylsulfonic acid sodium salt, sodium dodecyl sulfate, sodium lauryl diphenyl ether disulfonate, sodium dodecyl aliphatate, Pluronic F-127, polyethylene oxide¨polypropylene oxide¨polyethylene oxide (P123), sorbitan oleate (span-80), or a mixture thereof.
[0012] In a class of this embodiment, in (1), according to a mass ratio, the raw residue:
the surfactant: the water = 100: 0.5-5: 200-1000; and a grinding time is between 15 min and 120 min.
the surfactant: the water = 100: 0.5-5: 200-1000; and a grinding time is between 15 min and 120 min.
[0013] In a class of this embodiment, in (2), a mass fraction of the hydrochloric acid is between 20% and 25%; and, according to a mass ratio, the first intermediate residue: the hydrochloric acid 1: 8-20.
[0014] In a class of this embodiment, in (3), according to a mass ratio, the second intermediate residue: polyethyleneimine: ethanol = 10: 4-10: 200-1000 and a shaking time is between 0.5 h and 3 h.
[0015] In a class of this embodiment, in (4), according to a mass ratio, the third *
intermediate residue: nitric acid ¨ 1: 5-15 and a stirring time is between 0.5 h and 3 h.
intermediate residue: nitric acid ¨ 1: 5-15 and a stirring time is between 0.5 h and 3 h.
[0016] In a class of this embodiment, in (4), a grain size of the anode material for lithium-ion batteries ranges between 50 nm and 200 run, and a specific surface area of the anode material for lithium-ion batteries is between 15 m2/g and 25 m2/g.
[0017] In a class of this embodiment, in (1), a grain size of the raw residue after being ground is between 5 pm and 20 pm.
[0018] In a class of this embodiment, in (1), the chemical compositions and mass percentage thereof of the raw residue are as follows: C: 65-70%, Si02: 13-18%, CaO:
3-6%, A1203: 4-7%, Fe20: 1-2%, Na20: 1-2%, K20: 1-2% and a minute amount of impurities comprising MgO and ZnO.
3-6%, A1203: 4-7%, Fe20: 1-2%, Na20: 1-2%, K20: 1-2% and a minute amount of impurities comprising MgO and ZnO.
[0019] In a class of this embodiment, in (2), the first intermediate residue and the hydrochloric acid are stirred at a temperature of between 35 C and 45 C for between 0.5 h and 2 h.
[0020] Advantages of the method for preparing an anode material for lithium-ion , batteries using residues according to embodiments of the present disclosure are summarized as follows:
[0021] 1. The anode materials for lithium-ion batteries prepared by the invention have low ash content and small specific surface area, can reduce the boundary reaction during charge and discharge processes and have a small coulombic loss during the first charge.
Due to the nanoscale sphere diameter, the anode materials for lithium-ion batteries can be closely piled to form high-density electrodes and the spherical arrangement is good for intercalation and de-intercalation of lithium ions.
Due to the nanoscale sphere diameter, the anode materials for lithium-ion batteries can be closely piled to form high-density electrodes and the spherical arrangement is good for intercalation and de-intercalation of lithium ions.
[0022] 2. In addition to hard carbon materials, the anode materials for lithium-ion batteries prepared by the invention also contain a small amount of Si02 powder. The existence of Si02 powder reduces the irreversible capacity during the first charge.
However, the existence of Si02 powder reduces specific capacity. On the other hand, the micro structure of nanoscale carbon reduces the intercalation depth of lithium ions and shortens the intercalation process of lithium ions. The lithium ion can be intercalated between particle layers and in gaps between particles to improve the specific capacity of batteries, which just remedies the reduced specific capacity caused by the existence of Si02. For hard carbon materials, the larger irreversible capacity during the first charge is the main reason why lithium-ion batteries can't realize large-scale commercialization. The existence of SO2 powder of the invention remedies the shortcoming.
However, the existence of Si02 powder reduces specific capacity. On the other hand, the micro structure of nanoscale carbon reduces the intercalation depth of lithium ions and shortens the intercalation process of lithium ions. The lithium ion can be intercalated between particle layers and in gaps between particles to improve the specific capacity of batteries, which just remedies the reduced specific capacity caused by the existence of Si02. For hard carbon materials, the larger irreversible capacity during the first charge is the main reason why lithium-ion batteries can't realize large-scale commercialization. The existence of SO2 powder of the invention remedies the shortcoming.
[0023] 3. The anode materials for lithium-ion batteries prepared by the invention are hard carbon materials and are characterized by strong safety performance, good cycle performance (After 80 times of cycle, the capacity can still reach 72% of the initial capacity.) and high specific capacity (The initial specific capacity is 426triAhig). Since the pre-oxidation of the residues by HNO3 the modification of the residues by the dopant N are conducted during the preparation and no other impurities are introduced, the first-cycle coulombic efficiency exceeds 80%. Compared to other hard carbon materials, the first-cycle coulombic efficiency is improved greatly. The obtained anode materials for lithium-ion batteries are characterized by high capacity, high first-cycle coulombic efficiency, good cycle performance and good rate capability and are safe and pollution-free.
[0024] 4. The invention utilizes residues of biomass gasifiers of biomass synthetic oil refineries as materials to prepare anode materials for lithium-ion batteries.
Since the residues have a high content of carbon and are spherical microscopically, the preparation process doesn't need complicate chemical synthesis but only need purification and =
modification steps. Therefore, the invention gets rid of complicate intermediate synthetic steps of traditional anode material preparing processes, saves chemical raw materials and has an advantage in price in the market.
Since the residues have a high content of carbon and are spherical microscopically, the preparation process doesn't need complicate chemical synthesis but only need purification and =
modification steps. Therefore, the invention gets rid of complicate intermediate synthetic steps of traditional anode material preparing processes, saves chemical raw materials and has an advantage in price in the market.
[0025] 5. The residue materials used by the invention are waste from chemical processes and are low in cost. The recycling can reduce environment pollution.
The invention provides a clean renewable inexpensive new resource as raw materials for preparing hard carbon materials and an effective technical method to improve the first-cycle coulombic efficiency of hard carbon materials. The invention has a huge market advantage in terms of raw material sources, prices and product performance.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention provides a clean renewable inexpensive new resource as raw materials for preparing hard carbon materials and an effective technical method to improve the first-cycle coulombic efficiency of hard carbon materials. The invention has a huge market advantage in terms of raw material sources, prices and product performance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 is a SEM image of a residue from a biomass gasifier.
DETAILED DESCRIPTION OF THE EMBODIMENTS
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0027] For further illustrating the invention, experiments detailing a method for preparing an anode material for lithium-ion batteries using a residue from a biomass gasifier are described hereinbelow combined with the drawings. It should be noted that the following examples are intended to describe and not to limit the invention.
[0028] Residues in the embodiment are from a biomass gasifier of a biomass synthetic oil refinery. One source of the residues is detailed as follows: the ground biomass materials contact with reaction components in the gasifier, and then are taken out of the gasifier along with the gas products. The gas products are washed by water, and then the washing liquid is filtered to yield the residue. The chemical compositions and the mass ratios thereof of the residue are as follows: C: 65-70%, Si02: 13-18%, CaO: 3-6%, A1203:
4-7%, Fe203: 1-2%, Na20: 1-2%, K20: 1-2% and a minute amount of impurities including MgO and ZnO. As slaown in FIG 1, the residue from the biomass gasifiers are spherical microscopically.
Example 1
4-7%, Fe203: 1-2%, Na20: 1-2%, K20: 1-2% and a minute amount of impurities including MgO and ZnO. As slaown in FIG 1, the residue from the biomass gasifiers are spherical microscopically.
Example 1
[0029] A method for preparing an anode material for lithium-ion batteries using a residue from a biomass gasifier comprises the following steps:
=
=
[0030] mixing a raw residue, 1-hexadecylsulfonic acid sodium salt and de-ionized water according to a mass ratio of the raw residue to the 1-hexadecy1su1fonic acid sodium salt to the de-ionized water which is 100: 1: 500, putting the mixture of the raw residue, the 1-hexadecylsulfonic acid sodium salt and the de-ionized water to an agate mortar and grinding for 20 minutes, washing the mixture 3 times using de-ionized water to remove the 1-hexadecylsulfonic acid sodium sat, and filtering the mixture, to yield a first residue (intermediate product 1); adding hydrochloric acid with a mass fraction of 25%
to the first residue (intermediate product 1) according to a mass ratio of the first residue (intermediate product 1) to the hydrochloric acid which is 1: 10, stirring the mixture of the first residue (intermediate product 1) and the hydrochloric acid in a closed constant-temperature magnetic stirrer at a temperature of 40 C for 40 minutes to remove impurities, filtering, washing the mixture 4 times until the pH value of the solution is neutral, to yield a second residue (intermediate product 2); then, putting the second residue (intermediate product 2) in an ultrasonic oscillator, adding polyethyleneimine and ethanol to the second residue (intermediate product 2) according to a mass ratio of the second residue (intermediate product 2) to polyethyleneimine to ethanol which is 10: 5:
500, fully shaking the mixture of the second residue (intermediate product 2), polyethyleneimine and ethanol for 1 hour, washing the mixture 3 times to remove , polyethyleneimine and ethanol, filtering the mixture, to yield a third residue; finally, adding HNO3 having a mass fraction of 65% according to a mass ratio of the third residue to nitric acid which is 1: 5, stirring the mixture of the third residue and HNO3 in a closed environment at a temperature of 40 C for 30 minutes, fully washing the mixture 3 times, filtering and drying the mixture to obtain an anode material for lithium-ion batteries.
Table 1 lists the performance parameters of the anode material for lithium-ion batteries.
Example 2
to the first residue (intermediate product 1) according to a mass ratio of the first residue (intermediate product 1) to the hydrochloric acid which is 1: 10, stirring the mixture of the first residue (intermediate product 1) and the hydrochloric acid in a closed constant-temperature magnetic stirrer at a temperature of 40 C for 40 minutes to remove impurities, filtering, washing the mixture 4 times until the pH value of the solution is neutral, to yield a second residue (intermediate product 2); then, putting the second residue (intermediate product 2) in an ultrasonic oscillator, adding polyethyleneimine and ethanol to the second residue (intermediate product 2) according to a mass ratio of the second residue (intermediate product 2) to polyethyleneimine to ethanol which is 10: 5:
500, fully shaking the mixture of the second residue (intermediate product 2), polyethyleneimine and ethanol for 1 hour, washing the mixture 3 times to remove , polyethyleneimine and ethanol, filtering the mixture, to yield a third residue; finally, adding HNO3 having a mass fraction of 65% according to a mass ratio of the third residue to nitric acid which is 1: 5, stirring the mixture of the third residue and HNO3 in a closed environment at a temperature of 40 C for 30 minutes, fully washing the mixture 3 times, filtering and drying the mixture to obtain an anode material for lithium-ion batteries.
Table 1 lists the performance parameters of the anode material for lithium-ion batteries.
Example 2
[0031] A method for preparing an anode material for lithium-ion batteries using a residue from a biomass gasifier comprises the following steps:
[0032] mixing a raw residue, sodium dodecyl sulfate and de-ionized water according to a mass ratio of the raw residue to the 1-hexadecylsulfonic acid sodium salt to the de-ionized water which is 100: 2: 700, putting the mixture of the raw residue, the sodium dodecyl sulfate and the de-ionized water in an agate mortar and grinding for 40 minutes, washing the mixture 3 times using de-ionized water to remove the sodium dodecyl sulfate, and filtering the mixture, to yield a first residue (intermediate product 1);
adding hydrochloric acid with a mass fraction of 20% to the first residue (intermediate product 1) according to a mass ratio of the first residue (intermediate product 1) to the hydrochloric acid which is 1: 20, stirring the mixture of the first residue (intermediate product 1) and the hydrochloric acid in a closed constant-temperature magnetic stirrer at a temperature of 40 C for one hour to remove impurities, filtering, washing the mixture 4 times until the pH value of the solution is neutral, to yield a second residue (intermediate product 2);
then, putting the second residue (intermediate product 2) in an ultrasonic oscillator, adding polyethyleneinaine and ethanol to the second residue (intermediate product 2) according to a mass ratio of the second residue (intermediate product 2) to polyethyleneimine to ethanol which is 10: 8: 1000, fully shaking the mixture of the second residue (intermediate product 2), polyethyleneiraine and ethanol for 3 hours, washing the mixture 4 times to remove the polyethyleneimine and ethanol, filtering the mixture, to yield a third residue; finally, adding HNO3having a mass fraction of 55%
according to a mass ratio of the third residue to nitric acid which is 1: 8, stirring the mixture of the third residue and HNO3 in a closed environment at a temperature of 40 C
for one hour, fully washing the mixture 4 times, filtering and drying the mixture to obtain an anode material for lithium-ion batteries. Table 1 lists the performance parameters of the anode material for lithium-ion batteries.
Example 3
adding hydrochloric acid with a mass fraction of 20% to the first residue (intermediate product 1) according to a mass ratio of the first residue (intermediate product 1) to the hydrochloric acid which is 1: 20, stirring the mixture of the first residue (intermediate product 1) and the hydrochloric acid in a closed constant-temperature magnetic stirrer at a temperature of 40 C for one hour to remove impurities, filtering, washing the mixture 4 times until the pH value of the solution is neutral, to yield a second residue (intermediate product 2);
then, putting the second residue (intermediate product 2) in an ultrasonic oscillator, adding polyethyleneinaine and ethanol to the second residue (intermediate product 2) according to a mass ratio of the second residue (intermediate product 2) to polyethyleneimine to ethanol which is 10: 8: 1000, fully shaking the mixture of the second residue (intermediate product 2), polyethyleneiraine and ethanol for 3 hours, washing the mixture 4 times to remove the polyethyleneimine and ethanol, filtering the mixture, to yield a third residue; finally, adding HNO3having a mass fraction of 55%
according to a mass ratio of the third residue to nitric acid which is 1: 8, stirring the mixture of the third residue and HNO3 in a closed environment at a temperature of 40 C
for one hour, fully washing the mixture 4 times, filtering and drying the mixture to obtain an anode material for lithium-ion batteries. Table 1 lists the performance parameters of the anode material for lithium-ion batteries.
Example 3
[0033] A method for preparing an anode material for lithium-ion batteries using a .
residue from a biomass gasifier comprises the following steps:
residue from a biomass gasifier comprises the following steps:
[0034] mixing a raw residue, sorbitan oleate (span-80) and de-ionized water according to a mass ratio of the raw residue to the sorbitan oleate (span-80) to the de-ionized water which is 100: 4: 1000, putting the mixture of the raw residue, the 1-hexadecylsulfonic acid sodium salt and the de-ionized water into an agate mortar and grinding for one hour, washing the mixture 3 times using de-ionized water to remove the sorbitan oleate =
(span-80), and filtering the mixture, to yield a first residue (intermediate product 1);
adding hydrochloric acid with a mass fraction of 25% to the first residue (intermediate product 1) according to a mass ratio of the first residue (intermediate product 1) to the hydrochloric acid which is 1: 15, stirring the mixture of the first residue (intermediate product 1) and the hydrochloric acid in a closed constant-temperature magnetic stirrer at a temperature of 40 C for 1.5 hours to remove impurities, filtering, washing the mixture 4 times until the pH value of the solution is neutral, to yield a second residue (intermediate product 2); then, putting the second residue (intermediate product 2) in an ultrasonic oscillator, adding polyethyleneimine and ethanol to the second residue (intermediate product 2) according to a mass ratio of the second residue (intermediate product 2) to polyethyleneimine to ethanol which is 10: 4: 300, fully shaking the mixture of the second residue (intermediate product 2), polyethyleneimine and ethanol for 2 hours, washing the mixture 3 times to remove polyethyleneirnine and ethanol, filtering the washed mixture, to yield a third residue; finally, adding HNO3 having a mass fraction of 60%
according to a mass ratio of the third residue to nitric acid which is 1: 15, stirring the mixture of the third residue and 11\T03 in a closed environment at a temperature of 40 C for 1.5 hours, fully washing the mixture 4 times, filtering and drying the washed mixture to obtain an anode material for lithium-ion batteries. Table 1 lists the performance parameters of the anode material for lithium-ion batteries.
Table 1 Grain size Specific Discharge Impurity First-cycle Tap density coulornbic Examples d50 surface area capacity content (g/m1) efficiency (11m) (m2/g) (mAh/g) (%) (0/0 1 0.41 0.82 16.1 308 0.37 82.5 -2 0.20 0.75 21.3 318 0.25 82.8 3 0.29 0.80 18.7 291 0.28 81.3 BTR-CMB 11-22 1.1-1.4 0.6-2.6 110-340 ¨
Prior JFE-BAG-B2 10-20 1.1-1.45 0.5-2.5 354 art CMS 10-23 1.1-1.3 1.0-3.0 300-335 ¨
(span-80), and filtering the mixture, to yield a first residue (intermediate product 1);
adding hydrochloric acid with a mass fraction of 25% to the first residue (intermediate product 1) according to a mass ratio of the first residue (intermediate product 1) to the hydrochloric acid which is 1: 15, stirring the mixture of the first residue (intermediate product 1) and the hydrochloric acid in a closed constant-temperature magnetic stirrer at a temperature of 40 C for 1.5 hours to remove impurities, filtering, washing the mixture 4 times until the pH value of the solution is neutral, to yield a second residue (intermediate product 2); then, putting the second residue (intermediate product 2) in an ultrasonic oscillator, adding polyethyleneimine and ethanol to the second residue (intermediate product 2) according to a mass ratio of the second residue (intermediate product 2) to polyethyleneimine to ethanol which is 10: 4: 300, fully shaking the mixture of the second residue (intermediate product 2), polyethyleneimine and ethanol for 2 hours, washing the mixture 3 times to remove polyethyleneirnine and ethanol, filtering the washed mixture, to yield a third residue; finally, adding HNO3 having a mass fraction of 60%
according to a mass ratio of the third residue to nitric acid which is 1: 15, stirring the mixture of the third residue and 11\T03 in a closed environment at a temperature of 40 C for 1.5 hours, fully washing the mixture 4 times, filtering and drying the washed mixture to obtain an anode material for lithium-ion batteries. Table 1 lists the performance parameters of the anode material for lithium-ion batteries.
Table 1 Grain size Specific Discharge Impurity First-cycle Tap density coulornbic Examples d50 surface area capacity content (g/m1) efficiency (11m) (m2/g) (mAh/g) (%) (0/0 1 0.41 0.82 16.1 308 0.37 82.5 -2 0.20 0.75 21.3 318 0.25 82.8 3 0.29 0.80 18.7 291 0.28 81.3 BTR-CMB 11-22 1.1-1.4 0.6-2.6 110-340 ¨
Prior JFE-BAG-B2 10-20 1.1-1.45 0.5-2.5 354 art CMS 10-23 1.1-1.3 1.0-3.0 300-335 ¨
[0035] According to the performance parameters of the product of the invention and the current products, the anode materials for lithium-ion batteries prepared by the invention have the advantages that the specific capacity of the product of the invention is higher than the specific capacity of the current products, the grain size is nanoscale microsph,eres, the tap density is low, the content of impurities is low and the first-cycle coulornbic efficiency is high. The anode materials for lithium-ion batteries prepared by the invention meet the requirements of electrode materials for lithium-ion batteries.
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Claims (10)
1. A method for preparing an anode material for lithium-ion batteries, the method comprising:
(1) mixing a raw residue from a biomass gasifier and an aqueous solution comprising a surfactant to yield a mixed solution, grinding the mixed solution to disperse the raw residue, washing the mixed solution using water to remove the surfactant, leaching the mixed solution, to yield a first intermediate residue;
(2) adding hydrochloric acid to the first intermediate residue obtained in (1), stirring to remove impurities, filtering, and washing the residue to be neutral, to yield a second intermediate residue;
(3) adding polyethyleneimine and ethanol to the second intermediate residue obtained in (2), shaking to disperse the second intermediate residue, washing away the polyethyleneimine and the ethanol, filtering, to yield a third intermediate residue; and (4) adding nitric acid having a mass fraction of between 55% and 70% to the third intermediate residue obtained in (3), fully stirring at a temperature of between 35°C and 45°C for oxidation and modification, washing away the nitric acid, filtering and drying, to yield the anode material for lithium-ion batteries.
(1) mixing a raw residue from a biomass gasifier and an aqueous solution comprising a surfactant to yield a mixed solution, grinding the mixed solution to disperse the raw residue, washing the mixed solution using water to remove the surfactant, leaching the mixed solution, to yield a first intermediate residue;
(2) adding hydrochloric acid to the first intermediate residue obtained in (1), stirring to remove impurities, filtering, and washing the residue to be neutral, to yield a second intermediate residue;
(3) adding polyethyleneimine and ethanol to the second intermediate residue obtained in (2), shaking to disperse the second intermediate residue, washing away the polyethyleneimine and the ethanol, filtering, to yield a third intermediate residue; and (4) adding nitric acid having a mass fraction of between 55% and 70% to the third intermediate residue obtained in (3), fully stirring at a temperature of between 35°C and 45°C for oxidation and modification, washing away the nitric acid, filtering and drying, to yield the anode material for lithium-ion batteries.
2. The method of claim 1, characterized in that in (1), the surfactant is sodium dodecyl benzene sulfonate, 1-hexadecylsulfonic acid sodium salt, sodium dodecyl sulfate, sodium lauryl diphenyl ether disulfonate, sodium dodecyl aliphatate, Plutonic F-127, polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), sorbitan oleate (span-80), or a mixture thereof
3. The method of claim 1 or 2, characterized in that in (1), according to a mass ratio, the raw residue: the surfactant: the water = 100: 0.5-5: 200-1000; and a grinding time is between 15 min and 120 min.
4. The method of claim 1 or 2, characterized in that in (2), a mass fraction of the hydrochloric acid is between 20% and 25%; and, according to a mass ratio, the first intermediate residue: the hydrochloric acid = 1: 8-20.
5. The method of claim 1 or 2, characterized in that in (3), according to a mass ratio, the second intermediate residue: the polyethyleneimine: the ethanol =
10:
4-10: 200-1000 and a shaking time is between 0.5 h and 3 h.
10:
4-10: 200-1000 and a shaking time is between 0.5 h and 3 h.
6. The method of claim 1 or 2, characterized in that in (4), according to a mass ratio, the third intermediate residue: the nitric acid = 1: 5-15 and a stirring time is between 0.5 h and 3 h.
7. The method of claim 1 or 2, characterized in that in (4), a grain size of the anode material for lithium-ion batteries ranges between 50 nm and 200 nm, and a specific surface area of the anode material for lithium-ion batteries is between 15 m2/g and 25 m2/g.
8. The method of claim 1 or 2, characterized in that in (1), a grain size of the raw residue after being ground is between 5 µm and 20 µm.
9. The method of claim 1 or 2, characterized in that in (1), chemical compositions and mass percentage thereof of the raw residue are as follows: C: 65-70%, SiO2:
13-18%, CaO: 3-6%, Al2O3: 4-7%, Fe2O3: 1-2%, Na2O: 1-2%, K2O: 1-2%, and impurities comprising MgO and ZnO.
13-18%, CaO: 3-6%, Al2O3: 4-7%, Fe2O3: 1-2%, Na2O: 1-2%, K2O: 1-2%, and impurities comprising MgO and ZnO.
10. The method of claim 1 or 2, characterized in that in (2), the first intermediate residue and the hydrochloric acid are stirred at a temperature of between 35°C and 45°C for between 0.5 h and 2 h.
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PCT/CN2016/079380 WO2016169436A1 (en) | 2015-04-21 | 2016-04-15 | Method for preparing negative electrode material of lithium-ion battery by using biomass gasification furnace filter residue |
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CN105552372B (en) * | 2016-01-27 | 2018-02-13 | 太原理工大学 | A kind of N doped carbons microfiber material and its preparation method and application |
CN108630912B (en) * | 2018-03-11 | 2023-04-11 | 贵州中科星城石墨有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
CN108987720B (en) * | 2018-08-01 | 2021-02-12 | 吉林大学 | Carbon/zinc oxide composite material and preparation method and application thereof |
CN110112376B (en) * | 2019-03-25 | 2021-06-15 | 华南农业大学 | Preparation method and application of porous silicon oxide/carbon composite negative electrode material |
CN113528832A (en) * | 2021-07-12 | 2021-10-22 | 廊坊师范学院 | Method for green and efficient recovery of waste lithium ion battery anode material by using citrus fruits |
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JP4985410B2 (en) * | 1995-03-06 | 2012-07-25 | ソニー株式会社 | Method for producing negative electrode material for non-aqueous electrolyte secondary battery |
JP3531274B2 (en) * | 1995-04-20 | 2004-05-24 | 三菱化学株式会社 | Non-aqueous secondary battery |
JP3565994B2 (en) * | 1996-06-28 | 2004-09-15 | 呉羽化学工業株式会社 | Carbonaceous material for electrode of non-aqueous solvent secondary battery, method for producing the same, and non-aqueous solvent secondary battery |
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TW429638B (en) * | 1999-08-11 | 2001-04-11 | Fey George Ting Kuo | Preparations of negative electrode and carbon materials for secondary batteries |
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US8119288B2 (en) * | 2007-11-05 | 2012-02-21 | Nanotek Instruments, Inc. | Hybrid anode compositions for lithium ion batteries |
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CN102637920B (en) * | 2012-04-09 | 2014-07-30 | 中国科学院过程工程研究所 | Application of waste contact as lithium ion battery negative material |
CN102633251A (en) * | 2012-04-13 | 2012-08-15 | 西安交通大学 | Lithium ion battery cathode material prepared by blue carbon solid waste, and preparation method of lithium ion battery cathode material |
CN102709621A (en) * | 2012-05-24 | 2012-10-03 | 上海应用技术学院 | Method for recycling high purity carbon material from waste lithium ion battery |
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